Substantially oil soluble polyalkyl aromatic sulfonates



Patented Oct. 22, 1946 UNITED STATES PATENT OFFICE.

SUBSTANTIALLY' 01L SOLUBLE POLYALKYL AROMA-TIG SULFONATES Jacob Faust,Bellevillc, N. .L, assignor to L. Son

neborn Sons, Inc., a corporationoi Delaware.-

NDrawing;v Application December- 8, 1943; SerialNo. 513,469-

3 Claims. 1.

This; invention relates to new and useful improvements in substantiallyoil soluble polyalkyl aromatic sulfonates.

One object of the invention comprises, inter alia,. novel substantiallyoil. soluble polyalkyl aromatic sulfonates. possessing valuable.properties.

cordance with they invention essentially comprises.

from to 50% and preferably from m by Weight of a hydrocarbon materialcomprising at least one member selected. from the group con.- sisting ofpetroleum hydrocarbons and polyamyl naphthal'enes with at least threeamyl radicals,v and from to and preferably from 60.to-

70% by weight of a substantially oil soluble.

metaland preferably alkali metalpo1yamyl naphthalene sulfonate havingone MeSOa radical carried, by an unalkylated position of its.aromatioring.

Within the preferred, embodiment of: my, in-- vention by way of thenovel oleophilic hydrocarbon. composition I find it advisable to use apolyamyl naphthylene sulfonate carrying branched chain amyl groups..Although. individual poly.- amyl naphthalene sulfonates as for instancetritetra-or penta-amyl naphthalene sulfonates may be used, their mixtureis ordinarily more easilyavailable since it can be conveniently producedfrom commercial polyamyl naphthalene which. normally occurs as a mixtureof the, tri-, tetraand pentaproducts...

The petroleum hydrocarbon inaccordancewith the. invention may be. anysuitable petroleum, hy-. drocarbon or petroleum hydrocarbon. out. As isconventionally understood in the art, when ref; erence is made to theterm.petroleum hydrocar-. bon, such term includes not onlyindividualhydrocarbons: but. also mixtures. thereof,

Where the metal polyamyl naphthalene sulfonate in accordance with. theinvention. is. designated as being substantially oil soluble, I meanthereby that such product, as: is. well understood 2 in the art, issubstantially soluble in. petroleum spirits and oils, coal tar.solvents, chlorinated hydrocarbons and terpene hydrocarbons. Where useis made of the term oleophilic or such similar expression in designationof a hydrocarbon composition in accordance with the invention, I mean.to convey thereby the compatibility of my novel; hydrocarboncomposition. as such with the sol,-

vents or group ofv solvents just recited in sub-- stantially allproportions.

A suitable polyamyl naphthalene that maybe used for the preparation ofthe products in ac.- cordance with the invention, whether ashydrocarbonmaterial or as source for my novel polyamyl naphthalene sulfonates, is,for instance, the

commercial product constituting a light straw- I colored Viscous liquidessentially of the following 7 physical characteristics.

Specific gravity (24 C.) 0.922 Weight'per gallon 7.717 lbs. ViscositySaybolt at 100 F 4.73 secs. Viscosity Saybolt at 21.0" F 50 secs.

Viscosity index Minus 30 Flash point 350 F.

Fire point 410 F.

Pour point Below minus 10 F. Color (Lovibond /2'ce1l) 5Y1.5R Iodinevalue 28.2

Refractive index at 20 C 1.545

This commercial polyamyl naphthalene compound is ordinarily a mixture oftri-tetraand penta-amyl naphthalene in substantially the proportion, of-5-5. The amyl groups are in branched chain, that is they are attached.to methyl, propyl, and carbonyl configurations.

The polyamyl naphthalene sulfonates in accordance with the invention areobtained by subjecting a suitable polyamyl naphthalene of the requisitetype and characteristics or a mixture of such polyamyl naphthalenes tothe action of a sulfonating agent under sulfonating conditions.

The sulfonation reaction may be carried out in any suitable conventionalmanner such as, for instance, by treatment with gaseous S03 or by theaddition of fuming. sulfuric acid such as, for in-. stance, from 50 to.by Weight of a normal 20% fuming sulfuric; acid. In the latter ca theacid may be added as desired, either in a single treatment or in amultiple number of shots. In most cases and particularly with acidamounts approaching or equaling 100% the sulfonation pp oach s quanti eye ds, Itmay e .0 .1 times. advisable, dependent. upon special. condi-.tions. and treatments, to carry out; the, Sui-0 1 5:

tion reaction in. the presence of a substantially non-sulfonatableorganic solvent as, for instance, a suitable halogenated hydrocarbon,such as carbon tetrachloride, ethylene dichloride, amyl chloride,polyamyl chloride and chloroform.

Upon completion of the sulfonation reaction, the reaction mass isallowed to settle and such acid sludge as may have formed is withdrawn.The remaining layer is then suitably neutralized, preferably with theaid of an aqueous caustic solution such as aqueous caustic potash orsoda solution, to, for instance, phenol-phthaleine end point neutrality.The crude polyalkyl naphthalene sulfonate obtained may then be purifiedafter the removal of the aqueous layer, by for instance extraction with50% aqueous alcohol. Alternatively, the sulfonation mix may be dissolvedin benzol and the benzol solution may be thereupon washed with water tofree the same fromsalts, thereafter distilling clf the benzol andrecovering the purified product.

The polyamyl naphthalene sulfonates obtained in accordance with theinvention are substantially soluble in petroleum hydrocarbons even inthe cold and they are colloidally soluble in water. These novelsulfonate products, when incorporated into petroleum hydrocarbons,render the same substantially spontaneously emulsifiable in aqueousmedia without the use of any auxiliary linking agents or solvents andthe oleophilic hydrocarbon products containing the novel sulfonates inaccordance with the invention possess excellent foaming, wetting andpenetrating power.

Still further the polyamyl naphthalene sul- -fonates in accordance withthe invention are Valuable for textile processing and treating agents.They also constitute valuable agents as plasticizers in the preparationof synthetic rubber, conditioning agents for asphalts, dispersing aidsin paint and paint pigment compositions, dispersing agents forinsecticides and fungicides in agricultural sprays, assistants inleather processing and finishing, solubilizing agents for resins, dyesand other materials normally insoluble in oil and as ingredients incorrosion inhibiting and rust proofing compositions.

The following examples are furnished by way of illustration and not oflimitation:

Example I 50 parts by weight of oleum having a 20% S03 content wereslowly stirred into 100 parts by weight of a commercial polyamylnaphthalene of the description and properties hereinabove recited. Asulfonate mass formed which was allowed to settle at a temperature of140 to 150 F. A small amount of acid sludge was produced and was drawnoff, whereupon the upper layer was diluted with an equal volume ofbenzol and exactly neutralized with 20% caustic soda solution usingphenol-phthaleine as indicator. The resulting aqueous layer was allowedto settle and was then drawn oif. The remaining upper layer wasdistilled to remove the benzol, thus obtaining a puri fied product. Thepercent conversion to polyamyl naphthalene sulfonate was 55.5%. Theresulting product contained about 44% unreacted polyamyl naphthalene.

Example II 100 parts by weight of oleum having a 20% S03 content wereslowly stirred into 100 parts by Weight of a commercial polyamylnaphthalene of the description and properties hereinabove re- 4 cited; asulfonate mass formed which was allowed to settle at a temperature of140 to 150 F. A small amount of acid sludge was produced and was drawnofi, whereupon the upper layer was diluted with an equal volume ofbenzol and exactly neutralized with 20% caustic soda solution usingphenol-phthaleine indicator. The aqueous layer was allowed to settle anddrawn off. The

upper layer was distilled to remove the benzol, ob-

taining a purified product. The percent conversion to polyamylnaphthalene sulfonate was 90.4%. The resulting product was almost freefrom unreacted polyamyl naphthalene.

Example III To 100 parts by weight of the polyamyl naphthalene sulfonateproduct obtained in Example II were added 40 parts by weight of 100viscosity (Saybolt at 210 F.) Gulf Coast pale oil and the mixturestirred cold to obtain a homogeneous composition containingapproximately a polyamyl naphthalene sulfonate content of and an inerthydrocarbon carrier content of approximately 35%.

When only partially sulfonating a suitable polyamyl naphthalene, as isfor instance the case when using amounts of acid materially less thanthe resulting product may be recovered free from unreacted polyamylnaphthalene, or such unreacted polyamyl naphthalene may be left in theresulting sulfonate product, the latter to be used as such with theunreacted polyamyl naphthalene as a diluent therein. In such case, whenincorporating the polyamyl naphthalene sulfonate product in a suitablehydrocarbon oil within the scope of the invention, the unreactedpolyamyl naphthalene, depending upon the amount present, may be treatedas the sole hydrocarbon material or as part of the hydrocarbon materialto which the sulfonate is to be added in preparing the oleophilichydrocarbon composition in accordance with the invention.

The exceptionally high surface activity exercised by our noveloleophilic polyamyl naphthalene sulfonate hydrocarbon composition is,for example, shown by the product resulting from Example III, which in0.25% aqueous solution shows a wetting time (standard Draves test) ofabout two seconds and a surface tension of about 36.4 dynes per cm.

Another exceptional and valuable property of our novel sulfonatesresides in the fact that they are capable of emulsifying chlorinatedhydrocar bons, such as chloroform, carbon tetrachloride, dichlor ethylether and the like, to yield emulsions of an exceptionally high degreeof stability as is required, for example, in the use of such chlorinatedhydrocarbon emulsion for dormant agricultural sprays. None of thesechlorinated hydrocarbons has hitherto satisfactorily responded to suchemulsification by other wetting agents.

The properties and characteristics inherent in and exercised by thenovel polyamyl naphthalene sulfonates are substantially unaffected bythe particular hydrocarbon material with which they are compounded inaccordance with one of the embodiments of the invention and it istherefore in most cases immaterial whether the same is a petroleumhydrocarbon or unreacted polyamyl naphthalene. To this extent theproduct resulting, for instance, from Example I shows wetting andsurface tension characteristics of substantially the same order as thosehereinabove described as exhibited bythe productobtained in accordancewith Example II. One of the prime advantages inherent in the presence ofunreacted polyamyl naphthalene, however, whether present alone orpresent in conjunction with petroleum hydrocarbons, essentially residesin the ease of blendability with other components in the preparation ofcompositions to be compounded, for instance, for textile use, cuttingoil use and compositions for such other uses to which the polyamylnaphthalene sulfonates, as an ingredient in accordance with theinvention, may lend themselves. For this reason I find it often ofadvantage, within the scope of one preferred embodiment of my invention,to only partially sulfonate a polyamyl naphthalene in a manner yieldingfrom to 50% and preferably from to by weight of unreacted polyamylnaphthalene, and from to 75% and preferably from to by Weight ofpolyamyl naphthalene sulfonate of the herein described character andnature. Such a product results, for instance, when proceeding inaccordance With Example I. When desiring to obtain a product inaccordance with the invention containing in the requisite amounts onlyunreacted polyamyl naphthalene as the hydrocarbon material, it ispossible to achieve this result by using from 50 to of fuming sulfuricacid in the sulfonation treatment herein referred to.

The foregoing description is for purposes of illustration and not oflimitation and it is therefore our intention that the invention belimited only by the appended claims or theirequivalents wherein I haveendeavored to claim broadly all inherent novelty.

I claim:

1. A new substantially oil-soluble polyalkyl aromatic sulfonate whichconsists of a substantially oil soluble polyamyl naphthalene sulfonatehaving one metal sulfonate radical carried by an unalkylated position ofthe aromatic ring and having at least three amyl radicals.

2. A new substantially oil-soluble polyalkyl aromatic sulfonate inaccordance with claim 1 in which said polyamyl naphthalene sulfonatecarries branched chain amyl groups.

3. An oleophilic petroleum hydrocarbon composition which comprises from25 to 50% of a hydrocarbon material comprising at least one memberselected from .the group consisting of petroleum hydrocarbons andpolyamyl naphthalenes with at least three amyl radicals and from 50 to75% of a polyamyl naphthalene sulfonate having one metal sulfonateradical carried by an 1111- alkylated position of its aromatic ring andhaving at least three amyl radicals.

JACOB FAUST.

